Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049525/hk2341sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049525/hk2341Isup2.hkl |
CCDC reference: 1273736
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.005 Å
- R factor = 0.034
- wR factor = 0.108
- Data-to-parameter ratio = 14.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cu1 PLAT245_ALERT_2_C U(iso) H4A Smaller than U(eq) O4 by ... 0.01 AngSq PLAT480_ALERT_4_C Long H...A H-Bond Reported H5A .. S1 .. 3.06 Ang. PLAT481_ALERT_4_C Long D...A H-Bond Reported O5 .. S1 .. 3.84 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.29 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 9
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For general background, see: Desiraju (1995, 1997); Braga et al. (1998); Zaworotko (1997); Braga & Grepioni (2000); Moulton & Zaworotko (2001); Pan et al. (2001); Ma et al. (2001); Prior & Rosseinsky (2001). For bond-length data, see: Allen et al. (1987).
Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb. Lanthanum (III) nitrate hexahydrate (216.4 mg, 0.5 mmol), copper nitrate hexahydrate (295.6 mg, 1 mmol), 4-methylbenzene- sulfonic acid (344.4 mg, 2 mmol), ammonia (0.5 mol/l, 4 ml) and distilled water (10 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 443 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small blue crystals. These crystals were washed with distilled water followed by ethanol and allowed to air-dry at room temperature.
H atoms (for H2O) were located in difference syntheses and refined isotropically [O—H = 0.785 (17)–0.833 (17) Å and Uiso(H) = 0.058 (9) -0.080 (12) Å2]. The remaining H atoms were positioned geometrically, with C—H = 0.93 and 0.96 Å, for aromatic and methyl H atoms and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for aromatic H atoms.
In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to hydrogen-bonding interactions are of critical importance in biological systems, organic materials and coordination chemistry, hydrogen-bonding is currently the best tool in achieving this goal (Zaworotko, 1997; Braga & Grepioni, 2000). Supramolecular architectures are of considerable contemporary interest by virtue of their potential applications in various fields (Moulton & Zaworotko, 2001; Pan et al., 2001; Ma et al., 2001; Prior & Rosseinsky, 2001). We originally attempted to synthesize complexes featuring La and Cu metals chains by reaction of the lanthanum(III) and copper(II) ions with 4-methylbenzenesulfonic acid ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.
The asymmetric unit of the title compound, (I), (Fig. 1) contains one half cation and one anion, in which the bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).
In the crystal structure, intermolecular O—H···O and O—H···S hydrogen bonds (Table 1, Fig. 2) result in the formation of a supramolecular network structure; an intramolecular C—H···O hydrogen bond is also present.
For general background, see: Desiraju (1995, 1997); Braga et al. (1998); Zaworotko (1997); Braga & Grepioni (2000); Moulton & Zaworotko (2001); Pan et al. (2001); Ma et al. (2001); Prior & Rosseinsky (2001). For bond-length data, see: Allen et al. (1987).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).
[Cu(H2O)6](C7H7O3S)2 | F(000) = 534 |
Mr = 514.01 | Dx = 1.554 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5117 reflections |
a = 6.9472 (4) Å | θ = 2.4–28.3° |
b = 6.2891 (3) Å | µ = 1.24 mm−1 |
c = 25.1581 (14) Å | T = 273 K |
β = 91.565 (1)° | Prism, blue |
V = 1098.79 (10) Å3 | 0.48 × 0.37 × 0.20 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2349 independent reflections |
Radiation source: fine-focus sealed tube | 2004 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
φ and ω scans | θmax = 27.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.588, Tmax = 0.794 | k = −7→7 |
7237 measured reflections | l = −32→31 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0641P)2 + 0.4823P] where P = (Fo2 + 2Fc2)/3 |
2349 reflections | (Δ/σ)max < 0.001 |
158 parameters | Δρmax = 0.35 e Å−3 |
9 restraints | Δρmin = −0.42 e Å−3 |
[Cu(H2O)6](C7H7O3S)2 | V = 1098.79 (10) Å3 |
Mr = 514.01 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.9472 (4) Å | µ = 1.24 mm−1 |
b = 6.2891 (3) Å | T = 273 K |
c = 25.1581 (14) Å | 0.48 × 0.37 × 0.20 mm |
β = 91.565 (1)° |
Bruker SMART CCD area-detector diffractometer | 2349 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2004 reflections with I > 2σ(I) |
Tmin = 0.588, Tmax = 0.794 | Rint = 0.025 |
7237 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 9 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.35 e Å−3 |
2349 reflections | Δρmin = −0.42 e Å−3 |
158 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 0.0000 | 0.0000 | 0.04199 (16) | |
S1 | −0.01464 (9) | 0.60839 (10) | 0.90519 (3) | 0.04218 (18) | |
O1 | 0.1552 (3) | 0.5134 (3) | 0.93086 (9) | 0.0539 (5) | |
O2 | −0.0141 (3) | 0.8398 (3) | 0.90896 (8) | 0.0533 (5) | |
O3 | −0.1925 (3) | 0.5162 (3) | 0.92401 (9) | 0.0544 (5) | |
O4 | 0.7237 (3) | −0.1026 (4) | 0.04791 (11) | 0.0726 (7) | |
O5 | 0.5088 (3) | 0.2886 (3) | 0.03508 (9) | 0.0549 (5) | |
O6 | 0.3032 (4) | −0.1034 (4) | 0.05323 (11) | 0.0727 (7) | |
C1 | −0.0452 (5) | 0.6350 (7) | 0.74521 (14) | 0.0754 (10) | |
H1 | −0.0789 | 0.7348 | 0.7193 | 0.090* | |
C2 | −0.0544 (5) | 0.6913 (6) | 0.79850 (13) | 0.0639 (8) | |
H2 | −0.0946 | 0.8267 | 0.8081 | 0.077* | |
C3 | −0.0035 (4) | 0.5452 (5) | 0.83688 (11) | 0.0462 (6) | |
C4 | 0.0521 (5) | 0.3430 (5) | 0.82212 (12) | 0.0606 (7) | |
H4 | 0.0841 | 0.2424 | 0.8480 | 0.073* | |
C5 | 0.0601 (5) | 0.2907 (6) | 0.76879 (13) | 0.0702 (9) | |
H5 | 0.0985 | 0.1547 | 0.7592 | 0.084* | |
C6 | 0.0123 (5) | 0.4356 (7) | 0.72983 (13) | 0.0694 (9) | |
C7 | 0.0308 (6) | 0.3770 (9) | 0.67186 (14) | 0.0989 (15) | |
H7B | 0.1610 | 0.3353 | 0.6655 | 0.148* | |
H7A | −0.0025 | 0.4975 | 0.6501 | 0.148* | |
H7C | −0.0545 | 0.2611 | 0.6633 | 0.148* | |
H4A | 0.763 (4) | −0.220 (3) | 0.0485 (12) | 0.059 (10)* | |
H5A | 0.610 (3) | 0.340 (5) | 0.0462 (12) | 0.058 (9)* | |
H6A | 0.261 (5) | −0.220 (3) | 0.0575 (15) | 0.080 (12)* | |
H4B | 0.814 (4) | −0.020 (4) | 0.0558 (15) | 0.069 (11)* | |
H5B | 0.419 (3) | 0.342 (5) | 0.0480 (12) | 0.059 (10)* | |
H6B | 0.216 (4) | −0.017 (4) | 0.0593 (14) | 0.065 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0394 (2) | 0.0311 (3) | 0.0555 (3) | 0.00069 (16) | 0.00176 (18) | 0.00152 (17) |
S1 | 0.0414 (3) | 0.0320 (3) | 0.0532 (4) | 0.0005 (2) | 0.0027 (2) | −0.0004 (3) |
O1 | 0.0559 (11) | 0.0410 (11) | 0.0641 (12) | 0.0056 (8) | −0.0113 (10) | −0.0018 (8) |
O2 | 0.0529 (10) | 0.0318 (10) | 0.0754 (13) | 0.0002 (8) | 0.0044 (9) | −0.0022 (9) |
O3 | 0.0536 (11) | 0.0405 (11) | 0.0701 (13) | −0.0043 (8) | 0.0171 (10) | −0.0020 (8) |
O4 | 0.0691 (14) | 0.0359 (12) | 0.1105 (19) | 0.0052 (11) | −0.0400 (13) | 0.0005 (12) |
O5 | 0.0451 (11) | 0.0380 (11) | 0.0816 (14) | −0.0005 (9) | 0.0052 (10) | −0.0146 (9) |
O6 | 0.0746 (15) | 0.0363 (12) | 0.1095 (19) | −0.0008 (11) | 0.0460 (14) | 0.0054 (12) |
C1 | 0.067 (2) | 0.098 (3) | 0.0618 (19) | 0.007 (2) | −0.0002 (16) | 0.0239 (19) |
C2 | 0.0637 (18) | 0.059 (2) | 0.0689 (19) | 0.0101 (15) | 0.0047 (14) | 0.0124 (15) |
C3 | 0.0392 (12) | 0.0463 (15) | 0.0532 (15) | 0.0002 (11) | 0.0015 (11) | 0.0022 (11) |
C4 | 0.074 (2) | 0.0507 (18) | 0.0575 (16) | 0.0096 (14) | −0.0003 (14) | −0.0018 (14) |
C5 | 0.080 (2) | 0.069 (2) | 0.0618 (19) | 0.0039 (18) | 0.0046 (16) | −0.0145 (16) |
C6 | 0.0511 (17) | 0.099 (3) | 0.0579 (18) | −0.0072 (18) | 0.0023 (14) | −0.0035 (18) |
C7 | 0.085 (3) | 0.156 (5) | 0.056 (2) | −0.005 (3) | 0.0067 (18) | −0.008 (2) |
Cu1—O4i | 2.045 (2) | O6—H6B | 0.832 (17) |
Cu1—O4 | 2.045 (2) | C1—C6 | 1.375 (6) |
Cu1—O5 | 2.0182 (19) | C1—C2 | 1.390 (5) |
Cu1—O5i | 2.0182 (19) | C1—H1 | 0.9300 |
Cu1—O6i | 2.046 (2) | C2—C3 | 1.372 (4) |
Cu1—O6 | 2.046 (2) | C2—H2 | 0.9300 |
S1—O3 | 1.456 (2) | C3—C4 | 1.382 (4) |
S1—O1 | 1.458 (2) | C4—C5 | 1.384 (4) |
S1—O2 | 1.458 (2) | C4—H4 | 0.9300 |
S1—C3 | 1.768 (3) | C5—C6 | 1.373 (5) |
O4—H4A | 0.785 (17) | C5—H5 | 0.9300 |
O4—H4B | 0.833 (17) | C6—C7 | 1.513 (5) |
O5—H5A | 0.813 (17) | C7—H7B | 0.9600 |
O5—H5B | 0.786 (17) | C7—H7A | 0.9600 |
O6—H6A | 0.796 (17) | C7—H7C | 0.9600 |
O4i—Cu1—O4 | 180.00 (18) | Cu1—O6—H6A | 129 (3) |
O4—Cu1—O5i | 89.29 (9) | Cu1—O6—H6B | 115 (2) |
O4i—Cu1—O5i | 90.71 (9) | H6A—O6—H6B | 107 (2) |
O4—Cu1—O5 | 90.71 (9) | C6—C1—C2 | 121.7 (3) |
O4i—Cu1—O5 | 89.29 (9) | C6—C1—H1 | 119.2 |
O4i—Cu1—O6 | 88.59 (12) | C2—C1—H1 | 119.2 |
O4—Cu1—O6 | 91.41 (12) | C3—C2—C1 | 119.4 (3) |
O4i—Cu1—O6i | 91.41 (12) | C3—C2—H2 | 120.3 |
O4—Cu1—O6i | 88.59 (12) | C1—C2—H2 | 120.3 |
O5—Cu1—O5i | 180.00 (12) | C2—C3—C4 | 119.7 (3) |
O5—Cu1—O6i | 89.29 (9) | C2—C3—S1 | 121.1 (2) |
O5i—Cu1—O6i | 90.71 (9) | C4—C3—S1 | 119.2 (2) |
O5—Cu1—O6 | 90.71 (9) | C3—C4—C5 | 119.9 (3) |
O5i—Cu1—O6 | 89.29 (9) | C3—C4—H4 | 120.1 |
O6i—Cu1—O6 | 180.00 (12) | C5—C4—H4 | 120.1 |
O3—S1—O1 | 112.13 (13) | C6—C5—C4 | 121.3 (3) |
O3—S1—O2 | 112.14 (11) | C6—C5—H5 | 119.4 |
O1—S1—O2 | 112.30 (12) | C4—C5—H5 | 119.4 |
O3—S1—C3 | 106.67 (13) | C5—C6—C1 | 118.1 (3) |
O1—S1—C3 | 106.39 (12) | C5—C6—C7 | 120.1 (4) |
O2—S1—C3 | 106.72 (13) | C1—C6—C7 | 121.8 (4) |
Cu1—O4—H4A | 124 (2) | C6—C7—H7B | 109.5 |
Cu1—O4—H4B | 120 (2) | C6—C7—H7A | 109.5 |
H4A—O4—H4B | 109 (2) | H7B—C7—H7A | 109.5 |
Cu1—O5—H5A | 122 (2) | C6—C7—H7C | 109.5 |
Cu1—O5—H5B | 124 (2) | H7B—C7—H7C | 109.5 |
H5A—O5—H5B | 112 (3) | H7A—C7—H7C | 109.5 |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2 | 0.93 | 2.59 | 2.938 (4) | 103 |
O4—H4A···O1ii | 0.79 (2) | 2.00 (2) | 2.765 (3) | 166 (3) |
O6—H6A···O3iii | 0.80 (2) | 1.98 (2) | 2.772 (3) | 171 (4) |
O5—H5A···O1iv | 0.81 (2) | 1.95 (2) | 2.761 (3) | 175 (3) |
O5—H5A···S1iv | 0.81 (2) | 3.06 (2) | 3.839 (2) | 163 (3) |
O4—H4B···O2iv | 0.83 (2) | 1.98 (2) | 2.803 (3) | 167 (4) |
O5—H5B···O3v | 0.79 (2) | 1.96 (2) | 2.742 (3) | 176 (3) |
O6—H6B···O2v | 0.83 (2) | 1.98 (2) | 2.791 (3) | 166 (4) |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(H2O)6](C7H7O3S)2 |
Mr | 514.01 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 6.9472 (4), 6.2891 (3), 25.1581 (14) |
β (°) | 91.565 (1) |
V (Å3) | 1098.79 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.24 |
Crystal size (mm) | 0.48 × 0.37 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.588, 0.794 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7237, 2349, 2004 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.108, 1.03 |
No. of reflections | 2349 |
No. of parameters | 158 |
No. of restraints | 9 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.42 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).
Cu1—O4i | 2.045 (2) | Cu1—O5i | 2.0182 (19) |
Cu1—O4 | 2.045 (2) | Cu1—O6i | 2.046 (2) |
Cu1—O5 | 2.0182 (19) | Cu1—O6 | 2.046 (2) |
O4i—Cu1—O4 | 180.00 (18) | O4—Cu1—O6i | 88.59 (12) |
O4—Cu1—O5i | 89.29 (9) | O5—Cu1—O5i | 180.00 (12) |
O4i—Cu1—O5i | 90.71 (9) | O5—Cu1—O6i | 89.29 (9) |
O4—Cu1—O5 | 90.71 (9) | O5i—Cu1—O6i | 90.71 (9) |
O4i—Cu1—O5 | 89.29 (9) | O5—Cu1—O6 | 90.71 (9) |
O4i—Cu1—O6 | 88.59 (12) | O5i—Cu1—O6 | 89.29 (9) |
O4—Cu1—O6 | 91.41 (12) | O6i—Cu1—O6 | 180.00 (12) |
O4i—Cu1—O6i | 91.41 (12) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2 | 0.93 | 2.59 | 2.938 (4) | 103 |
O4—H4A···O1ii | 0.785 (17) | 1.997 (19) | 2.765 (3) | 166 (3) |
O6—H6A···O3iii | 0.796 (17) | 1.984 (18) | 2.772 (3) | 171 (4) |
O5—H5A···O1iv | 0.813 (17) | 1.950 (18) | 2.761 (3) | 175 (3) |
O5—H5A···S1iv | 0.813 (17) | 3.055 (18) | 3.839 (2) | 163 (3) |
O4—H4B···O2iv | 0.833 (17) | 1.98 (2) | 2.803 (3) | 167 (4) |
O5—H5B···O3v | 0.786 (17) | 1.958 (17) | 2.742 (3) | 176 (3) |
O6—H6B···O2v | 0.832 (17) | 1.98 (2) | 2.791 (3) | 166 (4) |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z+1. |
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In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to hydrogen-bonding interactions are of critical importance in biological systems, organic materials and coordination chemistry, hydrogen-bonding is currently the best tool in achieving this goal (Zaworotko, 1997; Braga & Grepioni, 2000). Supramolecular architectures are of considerable contemporary interest by virtue of their potential applications in various fields (Moulton & Zaworotko, 2001; Pan et al., 2001; Ma et al., 2001; Prior & Rosseinsky, 2001). We originally attempted to synthesize complexes featuring La and Cu metals chains by reaction of the lanthanum(III) and copper(II) ions with 4-methylbenzenesulfonic acid ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.
The asymmetric unit of the title compound, (I), (Fig. 1) contains one half cation and one anion, in which the bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987).
In the crystal structure, intermolecular O—H···O and O—H···S hydrogen bonds (Table 1, Fig. 2) result in the formation of a supramolecular network structure; an intramolecular C—H···O hydrogen bond is also present.